An ab initio study of hydrogen complexes of the X-H … π type between acetylene and HF or HCl
Identifieur interne : 003833 ( Main/Merge ); précédent : 003832; suivant : 003834An ab initio study of hydrogen complexes of the X-H … π type between acetylene and HF or HCl
Auteurs : Regiane C. M. U Araújo [Brésil] ; João Bosco P. Da Silva [Brésil] ; Mozart N. Ramos [Brésil]Source :
- Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy [ 1386-1425 ] ; 1994.
Abstract
Ab initio calculations are performed at the HF/6-311G, HF/6-311G∗∗, HF/6-311++G∗∗, MP2/6-311G∗∗ and MP2/6-311++G∗∗ theoretical levels to obtain geometries, H-bond energies and vibrational properties for the symmetrical T-shaped structures of hydrogen-bonded complexes involving acetylene (as the proton acceptor) and the halides HF and HCl (as the proton donors). The calculated H-bond lengths are a little overestimated at the Hartree-Fock level, whereas MP2 results are in very close agreement with the experimental values. For acetylene-HF the H-bond energy is predicted to be 11 kJ mol−1 at the HF level (including BSSE) and 19 kJ mol−1 at the MP2 level, indicating that the complex is more strongly bound than a simple van der Waals complex. The acetylene-HCl complex is less strongly bound than acetylene-HF, with a ΔE value of 5.8 kJ mol−1 at the HF/6-311++G∗∗ level (including BSSE) and of 13.2 kJ mol−1 at the MP2/6-311++G∗∗ level. The strengths of the H-bonds in both complexes can be interpreted in terms of intermolecular charge transfers by means of atomic charges derived from infrared intensity parameters. The intermolecular vibrational modes exhibit the usual effects of H-bond formation, which are an increased intensity in the X-H stretching of the proton-donor mode together with little change in the electron-donor spectrum. These normal modes are adequately interpreted in terms of the charge-charge flux-overlap modified model for infrared intensities. The new vibrational modes arising from complexation show several interesting features, especially the bending modes of the proton-donor molecule and the intermolecular stretching mode.
Url:
DOI: 10.1016/0584-8539(94)00194-G
Links toward previous steps (curation, corpus...)
- to stream Istex, to step Corpus: 000B81
- to stream Istex, to step Curation: 000963
- to stream Istex, to step Checkpoint: 002E72
Links to Exploration step
ISTEX:8BCFAE35706BA56A6E6FF9BCF46AF50DBE6D242DLe document en format XML
<record><TEI wicri:istexFullTextTei="biblStruct"><teiHeader><fileDesc><titleStmt><title>An ab initio study of hydrogen complexes of the X-H … π type between acetylene and HF or HCl</title><author><name sortKey="Araujo, Regiane C M U" sort="Araujo, Regiane C M U" uniqKey="Araujo R" first="Regiane C. M. U" last="Araújo">Regiane C. M. U Araújo</name></author><author><name sortKey="Da Silva, Joao Bosco P" sort="Da Silva, Joao Bosco P" uniqKey="Da Silva J" first="João Bosco P" last="Da Silva">João Bosco P. Da Silva</name></author><author><name sortKey="Ramos, Mozart N" sort="Ramos, Mozart N" uniqKey="Ramos M" first="Mozart N" last="Ramos">Mozart N. Ramos</name></author></titleStmt><publicationStmt><idno type="wicri:source">ISTEX</idno><idno type="RBID">ISTEX:8BCFAE35706BA56A6E6FF9BCF46AF50DBE6D242D</idno><date when="1995" year="1995">1995</date><idno type="doi">10.1016/0584-8539(94)00194-G</idno><idno type="url">https://api.istex.fr/document/8BCFAE35706BA56A6E6FF9BCF46AF50DBE6D242D/fulltext/pdf</idno><idno type="wicri:Area/Istex/Corpus">000B81</idno><idno type="wicri:Area/Istex/Curation">000963</idno><idno type="wicri:Area/Istex/Checkpoint">002E72</idno><idno type="wicri:doubleKey">1386-1425:1995:Araujo R:an:ab:initio</idno><idno type="wicri:Area/Main/Merge">003833</idno></publicationStmt><sourceDesc><biblStruct><analytic><title level="a">An ab initio study of hydrogen complexes of the X-H … π type between acetylene and HF or HCl</title><author><name sortKey="Araujo, Regiane C M U" sort="Araujo, Regiane C M U" uniqKey="Araujo R" first="Regiane C. M. U" last="Araújo">Regiane C. M. U Araújo</name><affiliation wicri:level="1"><country xml:lang="fr">Brésil</country><wicri:regionArea>Departamento de Química Fundamental, Universidade Federal de Pernambuco, 50739-901 Recife (PE)</wicri:regionArea><wicri:noRegion>50739-901 Recife (PE)</wicri:noRegion></affiliation></author><author><name sortKey="Da Silva, Joao Bosco P" sort="Da Silva, Joao Bosco P" uniqKey="Da Silva J" first="João Bosco P" last="Da Silva">João Bosco P. Da Silva</name><affiliation wicri:level="1"><country xml:lang="fr">Brésil</country><wicri:regionArea>Departamento de Química Fundamental, Universidade Federal de Pernambuco, 50739-901 Recife (PE)</wicri:regionArea><wicri:noRegion>50739-901 Recife (PE)</wicri:noRegion></affiliation></author><author><name sortKey="Ramos, Mozart N" sort="Ramos, Mozart N" uniqKey="Ramos M" first="Mozart N" last="Ramos">Mozart N. Ramos</name><affiliation wicri:level="1"><country xml:lang="fr">Brésil</country><wicri:regionArea>Departamento de Química Fundamental, Universidade Federal de Pernambuco, 50739-901 Recife (PE)</wicri:regionArea><wicri:noRegion>50739-901 Recife (PE)</wicri:noRegion></affiliation></author></analytic><monogr></monogr><series><title level="j">Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy</title><title level="j" type="abbrev">SAA</title><idno type="ISSN">1386-1425</idno><imprint><publisher>ELSEVIER</publisher><date type="published" when="1994">1994</date><biblScope unit="volume">51</biblScope><biblScope unit="issue">5</biblScope><biblScope unit="page" from="821">821</biblScope><biblScope unit="page" to="830">830</biblScope></imprint><idno type="ISSN">1386-1425</idno></series><idno type="istex">8BCFAE35706BA56A6E6FF9BCF46AF50DBE6D242D</idno><idno type="DOI">10.1016/0584-8539(94)00194-G</idno><idno type="PII">0584-8539(94)00194-G</idno></biblStruct></sourceDesc><seriesStmt><idno type="ISSN">1386-1425</idno></seriesStmt></fileDesc><profileDesc><textClass></textClass><langUsage><language ident="en">en</language></langUsage></profileDesc></teiHeader><front><div type="abstract" xml:lang="en">Ab initio calculations are performed at the HF/6-311G, HF/6-311G∗∗, HF/6-311++G∗∗, MP2/6-311G∗∗ and MP2/6-311++G∗∗ theoretical levels to obtain geometries, H-bond energies and vibrational properties for the symmetrical T-shaped structures of hydrogen-bonded complexes involving acetylene (as the proton acceptor) and the halides HF and HCl (as the proton donors). The calculated H-bond lengths are a little overestimated at the Hartree-Fock level, whereas MP2 results are in very close agreement with the experimental values. For acetylene-HF the H-bond energy is predicted to be 11 kJ mol−1 at the HF level (including BSSE) and 19 kJ mol−1 at the MP2 level, indicating that the complex is more strongly bound than a simple van der Waals complex. The acetylene-HCl complex is less strongly bound than acetylene-HF, with a ΔE value of 5.8 kJ mol−1 at the HF/6-311++G∗∗ level (including BSSE) and of 13.2 kJ mol−1 at the MP2/6-311++G∗∗ level. The strengths of the H-bonds in both complexes can be interpreted in terms of intermolecular charge transfers by means of atomic charges derived from infrared intensity parameters. The intermolecular vibrational modes exhibit the usual effects of H-bond formation, which are an increased intensity in the X-H stretching of the proton-donor mode together with little change in the electron-donor spectrum. These normal modes are adequately interpreted in terms of the charge-charge flux-overlap modified model for infrared intensities. The new vibrational modes arising from complexation show several interesting features, especially the bending modes of the proton-donor molecule and the intermolecular stretching mode.</div></front></TEI></record>Pour manipuler ce document sous Unix (Dilib)
EXPLOR_STEP=$WICRI_ROOT/Wicri/Musique/explor/MozartV1/Data/Main/Merge
HfdSelect -h $EXPLOR_STEP/biblio.hfd -nk 003833 | SxmlIndent | more
Ou
HfdSelect -h $EXPLOR_AREA/Data/Main/Merge/biblio.hfd -nk 003833 | SxmlIndent | more
Pour mettre un lien sur cette page dans le réseau Wicri
{{Explor lien
|wiki= Wicri/Musique
|area= MozartV1
|flux= Main
|étape= Merge
|type= RBID
|clé= ISTEX:8BCFAE35706BA56A6E6FF9BCF46AF50DBE6D242D
|texte= An ab initio study of hydrogen complexes of the X-H … π type between acetylene and HF or HCl
}}
| This area was generated with Dilib version V0.6.20. |  |